Thermoplastic elastomer carbon monoxide/olefin copolymers

ABSTRACT

Linear, thermoplastic, elastomeric copolymers comprise carbon monoxide and at least one olefinic C7- to C20-monomer and have an average molecular weight Mw greater than 15,000 g/mol and a Tg-value of less than -20° C., and comprise carbon monoxide, at least one olefinic C2- to C4-monomer and at least one olefinic C6- to C20-monomer and have an average molecular weight Mw greater than 40,000 g/mol and a Tg-value of less than 20° C.

The present invention relates to linear, thermoplastic, elastomericcopolymers of carbon monoxide and at least one olefinic C₇- toC₂₀-monomer, which have an average molecular weight M_(w) greater than15,000 g/mol and a T_(g)-value of less than −20° C.

The present invention furthermore relates to linear, thermoplastic,elastomeric copolymers of carbon monoxide, at least one olefinic C₂- toC₄-monomer and at least one olefinic C₆- to C₂₀-monomer, which have anaverage molecular weight M_(w) greater than 40,000 g/mol and aT_(g)-value of less than 20° C.

The present invention also relates to processes for the preparation ofsuch copolymers, the use of the copolymers for the production of fibers,films, moldings and coatings and to fibers, films, moldings and coatingsobtainable from the copolymers.

Carbon monoxide/ethylene copolymers and carbonmonoxide/ethylene/propylene terpolymers have very recently attractedinterest as engineering plastics for the production of articles having arelatively high melting point, for example gearwheels. As a rule, carbonmonoxide copolymers with ethylene as comonomer are very hard and brittleand have poor impact strength or none at all, so that they areunsuitable for many applications in which these properties aredesirable.

U.S. Pat. No. 5,352,767 describes alternating, elastomeric copolymers ofcarbon monoxide and α-olefins, which are prepared with the aid of acatalyst system which contains cationic metal complexes of group VIIIBof the Periodic Table of Elements and activators based on primary andsecondary alcohols.

However, the carbon monoxide/propylene, carbon monoxide/n-butene orcarbon monoxide/n-hexene copolymers described in said U.S. patent do nothave thermoplastic elastomeric properties even at average molecularweights M_(w) of up to 50,000 and are therefore unsuitable forapplications as engineering materials.

According to German Patent Application 196 10 358.4, it is known thatthe elastomer properties of said copolymers improve with increasingmolecular weight. These copolymers are industrially usable in generalonly at average molecular weights M_(w) in the region of 80,000 g/mol orhigher. However, it would be desirable to be able to realize wideindustrial use even in the case of lower molecular weights without, forexample, having to accept disadvantages with regard to theprocessability.

It is an object of the present invention to provide copolymers of carbonmonoxide and olefinic monomers, which copolymers have said disadvantagesonly to a minor degree if at all and can be prepared economically on anindustrial scale.

We have found that this object is achieved by linear, thermoplastic,elastomeric copolymers of carbon monoxide and at least one olefinic C₇-to C₂₀-monomer, which have an average molecular weight M_(w) greaterthan 15,000 g/mol and a T_(g)-value of less than −20° C.

We have also found linear, thermoplastic, elastomeric copolymers ofcarbon monoxide, at least one olefinic C₂- to C₄-monomer and at leastone olefinic C₆- to C₂₀-monomer, which have an average molecular weightM_(w) greater than 40,000 g/mol and a T_(g)-value of less than 20° C.

We have also found processes for the preparation of linear,thermoplastic, elastomeric copolymers of carbon monoxide and olefinicmonomers and the use of the copolymers for the production of fibers,films, moldings and coatings and the fibers, films, moldings andcoatings obtainable thereby.

The novel copolymers are composed of units which are based on themonomers carbon monoxide and one or more olefinically unsaturatedcompounds, ethylene, propylene, 1-butene, 1-pentene and 1-hexene beingexcluded in binary copolymers.

As a rule, the different monomer units strictly alternate in the novelbinary copolymers. In the case of the ternary and higher copolymersystems, the sequence of carbon monoxide and olefin components is as arule likewise strictly alternating, the relatively long-chain C₆- toC₂₀-alkene monomers being incorporated essentially randomly in thelinear copolymer chain, with regard to the suitable positions forincorporating olefins.

Suitable olefinically unsaturated compounds are in principle allmonomers of this class of compounds.

C₇- to C₂₀-alkenes, in particular C₇- to C₂₀-alk-1-enes, for example1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 1-hexadecene,1-octadecene and 1-eicosene, are preferably contained in binary carbonmonoxide copolymers. C₈- to C₂₀-alk-1-enes are particularly preferablyused.

The average molecular weights M_(w) of the novel binary carbon monoxidecopolymers are usually from 15,000 to 50,000 g/mol, but it is alsopossible to obtain copolymers having molecular weights of up to 70,000,100,000 or even 300,000 g/mol.

In the case of average molecular weights M_(w) (measured by the gelpermeation chromatography (GPC) method at 25° C. using Microstyragel(Waters) as column material and chloroform as solvent against apolystyrene standard) greater than 15,000 g/mol, T_(g)-values of lessthan −20° C. are achieved with the novel binary copolymers. The binarycopolymers preferably have T_(g)-values of less than −30° C. Dependingon the choice of the olefinic comonomer, even T_(g)-values in the regionof −60° C. are obtained. The melting points of these copolymers areusually from −7 to 45° C. Novel copolymers of carbon monoxide andrelatively long-chain olefinic monomers, such as 1-octadecene and1-eicosene, have two melting points, indicating semicrystalline segmentsin the region of the nonpolar side chains along the linear copolymerchain. By incorporating ¹³CO into binary copolymers with, for example1-eicosene as an olefin component, it was found that more than 50% ofthe novel copolymer chains are linked regioselectively head-to-tail.

Suitable olefinic C₆- to C₂₀-monomers for non-binary copolymers, inparticular ternary copolymers, of carbon monoxide, an olefinic C₂- toC₄-monomer and an olefinic C₆- to C₂₀-monomer are in particular C₆- toC₂₀-alk-1-enes, for example 1-hexene, 1-heptene, 1-octene, 1-nonene,1-decene, 1-dodecene, 1-hexadecene, 1-octadecene or 1-eicosene.1-Octene, 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene and1-eicosene are preferably used. 1-Octadecene and 1-eicosene areparticularly preferred. Preferably used olefinic C₂- to C₄-monomers arepropylene and buty-1-ene, in particular propylene.

In addition to the abovementioned alkenes, suitable olefinicallyunsaturated compounds are conjugated or isolated C₆- to C₂₀-dienes, forexample 1,4-hexadiene and 1,5-hexadiene.

Carbon monoxide/propylene/C₆- to C₂₀-alk-1-ene terpolymers, such ascarbon monoxide/propylene/1-decene, carbonmonoxide/propylene/1-dodecene, carbon monoxide/propylene/1-hexadecene-,carbon monoxide/propylene/1-octadecene and carbonmonoxide/propylene/1-eicosene terpolymers, are preferred. The content ofstructural units which is based on propylene in the carbonmonoxide/propylene/C₆- to C₂₀-terpolymers is in general from 0.1 to 70,preferably from 5 to 60, in particular from 10 to 50, mol %, based onthe terpolymer. Particularly suitable terpolymers having these propylenecontents are carbon monoxide/propylene/1-octadecene and carbonmonoxide/propylene/1-eicosene terpolymers.

The novel terpolymers have, as a rule, an average molecular weight M_(w)greater than 40,000 g/mol and a T_(g)-value of less than 20° C.,preferably less than −10° C. Terpolymers having an average molecularweight M_(w) up to 70,000, 170,000, 300,000 and even 500,000 g/mol arealso obtainable.

The novel bindery carbon monoxide copolymers and the carbonmonoxide/propylene terpolymers are, for example, readily soluble intetrahydrofuran, toluene, dichloromethane and chloroform.

The molar ratio of carbon monoxide to the sum of the structural unitsbased on the olefinically unsaturated monomers in the novel binary andhigher carbon monoxide copolymers is in general 1:1.

The novel copolymers have thermoplastic elastomeric properties.

The molecular weight distribution M_(w)/M_(n) (weight averagevalue/number average value) of the novel copolymers, measured by the gelpermeation chromatography (GPC) method analogously to the abovedescription, is in general from 1.2 to 3.5, preferably less than 2.5.

The incorporation of relatively long-chain 1-olefin monomer buildingblocks in, for example, binary and ternary carbon monoxide copolymersalso influences the polarity of films, fibers, moldings and coatingsobtainable from these copolymers. These materials have lower surfacetension than conventional carbon monoxide/ethylene or carbonmonoxide/propylene copolymers. Accordingly, hydrophobic materialsurfaces can be obtained using the novel binary carbon monoxide/C₈- toC₂₀-alkenes. This property can be determined, for example, with the aidof the sessile drop technique, described in R. J. Good, and R. R.Shomberg, “Surface and Colloid Science”, Vol. 11, Experimental Methods,Plenum Press, New York, 1979. For example a Θ-value of 110.27° wasobtained for a water drop applied to a film of novel carbonmonoxide/1-octene copolymers. Materials having hydrophobic surfacebehavior can also be made available from the novel carbon monoxidepropylene terpolymers. The degree of hydrophobic surface behaviorbetween the limits for pure carbon monoxide/propylene and pure carbonmonoxide/relatively long-chain olefin copolymers can be establishedthrough the proportion of long-chain olefins in the terpolymer. Polymerfilm materials obtainable in the terpolymerization of carbon monoxideand propylene with 1-octadecene and containing 13% by weight of1-octadecene give a Θ-value of 91.3° in the measurement of the contactangle. This value is considerably higher than that for carbonmonoxide/propylene copolymers (Θ=83.03°), but lower than that for carbonmonoxide/octadecene copolymers (Θ=107.14°). The alkyl side chains may bearranged in a tubular manner around the polar carbon monoxide backboneand thus cause the change from hydrophilic to hydrophobic behavior. Thesurface polarity of the fibers, films, moldings and coatings obtainedcan thus be established in accordance with the specific requirements ofthe application by the choice of the long-chain olefinic monomer andthrough the proportion of relatively long-chain olefinic monomers whichis incorporated into the copolymer.

Owing to their toughening properties and their biocompatible behavior,the novel polymer materials have a wide range of potential uses, forexample in polymer blend technology or medical technology.

For the preparation of the novel linear, thermoplastic, elastomericcopolymers carbon monoxide can be copolymerized with olefinicallyunsaturated compounds in a virtually alcohol-free or anhydrouspolymerization medium in the presence of a catalyst whose activematerial is formed from

A) a metal complex of the formula (I)

where:

M is a metal of group VIIIB of the Periodic Table of Elements

E¹ and E² are each an element from group VA of the Periodic Table ofElements,

Z is a bridging structural unit comprising one, two, three or foursubstructural units of elements of group IVA, VA or VIA of the PeriodicTable of Elements,

R¹ to R⁴ are substituents selected from the group consisting of organicC₁- to C₂₀-radicals and C₃- to C₃₀-organosilicon radicals, it beingpossible for the radicals to contain an element or a plurality ofelements of group IVA, VA, VIA and VIIA of the Periodic Table ofElements,

L¹ and L² are formally uncharged Lewis base ligands

X is a monovalent or divalent anion

m and n are each 1 or 2

and m×n=2 and

B) an activator component which contains a hydroxyl group in themolecule and which is used in an amount of from 0 to 500 moleequivalents, based on M in (I).

A further process for the preparation of the novel linear, thermoplasticor elastomeric copolymers is the copolymerization of carbon monoxidewith olefinically unsaturated compounds in a virtually alcohol-free oranhydrous polymerization medium in the presence of a catalyst whoseactive material is formed from

a) a salt of a metal M of group VIIIB of the Periodic Table of Elements,

b) a compound or a plurality of compounds selected from the groupconsisting of the protic acids and Lewis acids,

c) a chelate compound of the formula (II)

 R¹R²E¹—Z—E²R³R⁴  (II),

where:

E¹ and E² are each an element of group VA of the Periodic Table ofElements,

Z is a bridging structural unit comprising one, two, three or foursubstructural units of elements of group IVA, VA or VIA of the PeriodicTable of Elements, and

R¹ to R⁴ are substituents selected from the group consisting of theorganic C₁- to C₂₀-radicals and C₃- to C₃₀-organosilicon radicals, itbeing possible for the radicals to contain an element or a plurality ofelements of group IVA, VA, VIA and VIIA of the Periodic Table ofElements, and,

d) an activator component B), which contains a hydroxyl group in themolecule and is used in an amount of from 0 to 500 mol equivalents,based on M in (I).

The polymerizations for the preparation of the novel carbon monoxidecopolymers can be carried out both batchwise and continuously in thepresence of a polymerization catalyst comprising A), or a), b), c) andoptionally B) or d).

Suitable polymerization catalysts are metal compounds of the eighthsubgroup of the Periodic Table of Elements (VIIIB), which are present asdefined metal complexes (I) or can be formed in situ from a metal salta) of the metals of group VIIIB of the Periodic Table of Elements,protic and/or Lewis acids b) and a chelate compound c) of the formula(II). If required, the activators B) or d) may be added to the metalcompounds.

Suitable metals M are the metals of group VIIIB of the Periodic Table ofElements, i.e., in addition to iron, cobalt and nickel, mainly theplatinum metals such as ruthenium, rhodium, osmium, iridium and platinumand very particularly palladium. The metals nickel, palladium andplatinum are present in general with a formal double positive charge,the metals cobalt, rhodium and iridium in general with a formal singlepositive charge and the metals iron, ruthenium and osmium in generalformally uncharged in the complexes.

Suitable elements E¹ and E² of the chelate ligands, also referred tobelow as chelate compound (II), are the elements of main group V of thePeriodic Table of Elements (group VA), i.e. nitrogen, phosphorus,arsenic, antimony or bismuth. Particularly suitable are nitrogen andphosphorus, in particular phosphorus. The chelate ligand or the chelatecompound (II) may contain different elements E¹ and E², for examplenitrogen and phosphorus, but it preferably contains identical elementsE¹ and E², and in particular E¹ and E² are each phosphorus.

The bridging structural unit Z is an atom group which links the twoelements E¹ and E² to one another. The substructural units comprising anatom or a plurality of atoms bonded to one another from the group IVA,VA or VIA of the Periodic Table of Elements usually form the bridgebetween E¹ and E². Possible free valences of these bridge atoms can besaturated in various ways, for example by substitution by hydrogen or byelements of group IVA, VA, VIA or VIIA of the Periodic Table ofElements. These substituents may form ring structures with one anotheror with the bridge atom.

Suitable bridging structural units Z are those comprising one, two,three or four elements of group IVA of the Periodic Table of Elementssuch as methylene (—CH₂—), 1,2-ethylene (—CH₂—CH₂—), 1,3-propylene(—CH₂—CH₂—CH₂—), 1,4-butylene, 1,3-disilapropylene (—R⁵R⁶Si—CH₂—SiR⁵R⁶—,where R⁵ and R⁶ are each C₁- to C₁₀-alkyl or C₆- to C₁₀-aryl),ethylidene (CH₃(H)C═), 2-propylidene ((CH₃)₂C═), diphenylmethylene((C₆H₅)₂C═) or ortho-phenylene.

Examples of particularly suitable bridging structural units are1,2-ethylene, 1,3-propylene and 1,4-butylene.

Suitable organic carbon radicals R¹ to R⁴ are, independently of oneanother, aliphatic and cycloaliphatic and aromatic radicals of 1 to 20carbon atoms, for example methyl, ethyl, 1-propyl, 1-butyl, 1-pentyl,1-hexyl and 1-octyl and their structural analogs. Linear arylalkylgroups having 1 to 10 carbon atoms in the alkyl radical and 6 to 20carbon atoms in the aryl radical are also suitable, for example benzyl.Further radicals R¹ to R⁴ which may be mentioned are aryl radicals, forexample, toluyl, anisyl, preferably ortho-anisyl, xylyl and othersubstituted phenyl groups, in particular phenyl.

Suitable cycloaliphatic radicals are C₃- to C₁₀-monocyclic systems, suchas cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl, thelast-mentioned one being particularly preferred.

Suitable branched aliphatic radicals are C₃- to C₂₀-alkyl, preferablyC₃- to C₁₂-alkyl, such as isopropyl, isobutyl, sec-butyl, neopentyl andtert-butyl.

Particularly suitable branched aliphatic radicals are tert-butyl,isopropyl and sec-butyl.

Alkyl groups having a branch lying further outside are also suitable assubstituents R¹ to R⁴, such as isobutyl, 3-methyl-but-2-yl and4-methylpentyl.

R¹ to R⁴ may, independently of one another, also contain atoms fromgroup IVA, VA, VIA or VIIA of the Periodic Table of Elements, forexample halogen, oxygen, sulfur, nitrogen or silicon, in this case, forexample, bis(trimethylsilyl)methyl. Functional groups which are inertunder the polymerization conditions are also suitable in thisconnection.

Preferred heterosubstituents R¹ to R⁴ are C₃- to C₃₀-organosiliconradicals, i.e. tetravalent silicon atoms which on the one hand arebonded to E¹ or E² and whose other valences are saturated with threeorganic carbon radicals, the sum of the carbon atoms of these threeradicals bonded to silicon being from three to thirty. Examples aretrimethylsilyl, tert-butyldimethylsilyl and tri-phenylsilyl, inparticular triamethylsilyl.

1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane and1,4-bis(diphenylphosphino)butane are preferably used as chelate ligandor chelate compound (II).

Very particularly preferred compounds as chelate ligand or chelatecompound (II) are 1,3-bis(diphenylphosphino)propane and1,4-bis(diphenylphosphino)butane.

Suitable formally uncharged ligands L¹ and L² are in general Lewisbases, i.e. compounds, preferably organic compounds or water, having atleast one free electron pair, alkanols or phenols generally beingunsuitable.

Lewis bases whose free electron pair or whose free electron pairs is orare present on a nitrogen or oxygen atom, i.e. nitriles, R—CN, ketones,ethers or preferably water, are suitable.

Examples of suitable Lewis bases are C₁- to C₁₀-nitriles, such asacetonitrile, propionitrile or benzonitrile, or C₃- to C₁₀-ketones, suchas acetone or acetylacetone, or C₂- to C₁₀-ethers, such as dimethylether, diethyl ether or tetrahydrofuran.

Particularly for catalysts which require no activator B) or d), suitableligands L¹ and L² are those of the formula (III)

T—OH  (III)

Here, T is hydrogen or an organic C₁- to C₁₅-radical provided with aLewis base group. Suitable organic C₁- to C₁₅-radicals T are, forexample, linear or cyclic CH₂_(n)-units, where n is from 1 to 10, i.e.methylene, 1,2-ethylene, 1,3-propylene, 1,4-butylene, 1,5-pentylene,1,6-hexylene, 1,7-heptylene, 1,8-octylene, 1,9-nonylene or1,10-decylene.

Suitable Lewis base groups are ether, ester, ketone, amine, phosphaneand in particular nitrile (—C≡N) or tertiary amine.

Suitable compounds T—OH are, for example, water or α,ω-hydroxynitriles,such as NC CH₂_(n)OH where n is from 1 to 10, or(2-hydroxymethyl)tetrahydrofuran, and (2-hydroxymethyl)(N-organo)pyrrolidines (IIIa) or (2-hydroxymethyl)(N-organo)piperidines(IIIb)

where R′ is C₁- to C₁₀-alkyl or C₃- to C₁₀-cycloalkyl, for example,methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl,tert-butyl, cyclopentyl or cyclohexyl. R′ may furthermore be C₆- toC₁₀-aryl, such as phenyl, naphthyl.

In general, the ligands T—OH, except for water, are bonded to the metalM in (I) via the Lewis base group defined above.

Suitable anions X in (I) are, for example, perchlorate, sulfate,phosphate, nitrate, carboxylates, for example acetate, trifluoroacetate,trichloroacetate, propionate, oxalate, citrate and benzoate, andconjugated anions of organosulfonic acids, for example methylsulfonate,trifluoromethylsulfonate and p-toluenesulfonate, and furthermoretetrafluoroborate, tetraphenylborate, tetrakis(pentafluorophenyl)borate,hexafluorophosphate, hexafluoroarsenate or hexafluoroantimonate.Perchlorate, trifluoroacetate, sulfonates, such as methylsulfonate,trifluoromethylsulfonate and p-toluenesulfonate, tetrafluoroborate andhexafluorophosphate are preferably used as anion X, in particulartrifluoroacetate, perchlorate or p-toluenesulfonate.

Examples of particularly suitable metal complexes (I) are(bis-1,3(diphenylphosphino)propanepalladiumbisacetonitrile)bis(tetrafluoroborate) ({circumflex over (=)}[Pd(dppp)(NCCH₃)₂](BF₄)₂,dppp=1,3(diphenylphosphino)propane),(bis-1,3(diphenylphosphino)propanepalladiumbisaquo)bis(tetrafluoroborate),1,3(diphenylphosphino)-propanepalladiumbis(3-hydroxypropionitrile)bis(tetrafluoroborate),(bis-1,4(diphenylphosphino)butanepalladiumbisacetonitrile)bis(tetrafluoroborate) and(bis-1,4-(diphenylphosphino)butanepalladiumbisaquo)bis(tetrafluoroborate).

The metal complexes of the formula (I) were prepared in general byprocesses known from the literature, as described in Makromol. Chem.1993, 194, p. 2579. Usually, tetrakis-ligand metal complexes, such astetrakis-acetonitrilepalladium bistetrafluoroborate, can be reacted withchelate compounds (II) and the ligands L¹ and L² or TOH to give themetal complexes (I). A preferred process for the preparation of aquocomplexes (I) is the reaction of the chelatephosphene-acetonitrile-metalcomplexes with water. The reaction is carried out in general in asolvent, for example dichloromethane, acetonitrile or water, at from −78to 40° C.

In the in situ generation of the polymerization catalysts, the metals Mare usually used in the divalent state in the form of their salts andare brought into contact with the chelate compound c) of the generalformula (II) and the acids b). This can be done before the catalyticallyactive material thus obtainable is brought into contact with the monomerand any further activator d), in general outside the polymerizationreactor. The reaction of the individual components metal salt a),chelate compound c) of the formula (II), acid b) and, if required,activator components d) can however also be carried out in thepolymerization reactor, in the presence of the monomers.

Suitable salts of usually divalent metals M are halides, sulfates,phosphates, nitrates and carboxylates, such as acetates, propionates,oxalates, citrates and benzoates, and sulfonic acid salts, for examplemethylsulfonates, trifluoromethylsulfonate and p-toluenesulfonate.Carboxylates, sulfonic acid derivatives and in particular acetates arepreferably used.

Particularly suitable catalyst components a) are palladiumdicarboxylates, preferably palladium diacetate, palladium dipropionate,palladium bis(trifluoroacetate) and palladium oxalate, and palladiumsulfonates, preferably palladium bis(trifluoromethanesulfonate),palladium bis(methanesulfonate) and palladium bis(p-toluenesulfonate),in particular palladium diacetate being used.

Lewis acids and protic acids and mixtures thereof may be used ascatalyst components b).

Suitable protic acids b) are strong mineral acids, preferably having apKa- of less than 3, sulfuric acid and perchloric acid, and strongorganic acids, for example trichloroacetic and trifluoroacetic acid andsulfonic acids, methanesulfonic acid, p-toluenesulfonic acid andbenzenesulfonic acid.

Furthermore, the acidic salts of strong acids with weak bases, forexample ammonium salts of the abovementioned acids, are suitable.

Examples of suitable Lewis acids are halides of the elements of groupIIIA of the Periodic Table of Elements, for example boron trifluoride,boron trichloride, aluminum trifluoride and aluminum trichloride,halides of the elements of group VA of the Periodic Table of Elements,such as phosphorus pentafluoride, and antimony pentafluoride, andhalides of the metals of the subgroup IVB of the Periodic Table ofElements, such as titanium tetrachloride or zirconium tetrachloride.Further suitable Lewis acids are organically substituted Lewis acids,for example tris(pentafluorophenyl)borane.

Preferably used Lewis acids are boron trifluoride, antimonypentafluoride and tris(pentafluorophenyl)borane.

Particularly preferred components b) are those which have a weaklycoordinating conjugated anion, i.e. an anion which forms only a weakbond to the central metal of the complex, such as tetrafluoroborate,hexafluorophosphate, perchlorate, trifluoroacetate,trifluoromethylsulfonate, p-tosylate and borates, such aspyrocatecholatoborate and tetraarylborate, a suitable aryl group beingin particular 2,5-dimethylphenyl, 2,5-ditrifluoromethylphenyl orpentafluorophenyl.

Other suitable catalyst components a) and b) are those generally knownfor systems with bisphosphines from EP-A 501 576 and 516 238.

Catalyst systems contain, as component c), a chelate compoundR¹R²E¹—Z—E²R³R⁴ (II), which has already been described in the discussionof the metal complexes (I).

The ratio of the catalyst components a), b) and c) to one another ischosen in general so that the molar ratio of the metal compound a) toacid b) is from 0.01:1 to 100:1, preferably 0.1:1 to 1:1, and the molarratio of the metal compound a) to the component c) is from 0.01:1 to10:1, preferably from 0.1:1 to 2:1.

The activator component B) or d) is as a rule a chemical compound whichcontains at least one hydroxyl group in the molecule. This includes inparticular C₁- to C₁₀-alcohols, such as methanol, ethanol, n-propanol,isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol,n-hexanol, n-octanol, n-decanol, cyclohexanol, phenol and water.Methanol and/or water are preferably used as activator component B) ord).

The molar ratio of activator component B) or d) to metal M is from 0 to500, preferably from 0 to 300. It has proven advantageous not to exceedthe maximum ratio in the polymerization reaction, since otherwise theaverage molecular weights Mw of the carbon monoxide copolymers may betoo low.

The addition of the activator B) or d) is superfluous only when thecatalyst contains, as Lewis base ligands L¹, L² those which contain ahydroxyl group in the molecule and which have been defined more exactlyabove by the formula T—OH (III).

Pressures of from 100 to 500,000, are preferably from 500 to 350,000 andin particular from 1000 to 10,000, kPa, at temperatures from −50 to 400°C., preferably from 10 to 250° C. and in particular from 20 to 100° C.have proven suitable reaction parameters for the preparation of linear,thermoplastic, elastomeric copolymers from carbon monoxide andolefinically unsaturated compounds.

The polymerization reactions can be carried out in the gas phase in afluidized bed or with stirring, or in suspension, in liquid and insupercritical monomers and in the solvents which are inert under thepolymerization conditions.

The polymerization reactions can be carried out in a virtuallyalcohol-free or anhydrous polymerization medium. This means that, exceptfor possibly the activator component B) or d), no further amount ofalcohol or water was or is added to the reaction mixture comprisingmonomers, catalysts, and, if required, inert solvent or suspendingmedium.

Suitable inert solvents and suspending media are those which contain nohydroxyl group in the molecule, i.e. ethers, such as diethyl ether ortetrahydrofuran, aromatic solvents, such as benzene, toluene,ethylbenzene or chlorobenzene, aliphatic hydrocarbons, such asisobutane, or chlorinated aliphatic hydrocarbons such as dichloromethaneor 1,1,1-trichloromethane, or mixtures of said compounds.

Initially taking the catalyst in the inert solvent, if requiredsubsequently adding the activator component B) or d) and then adding themonomers and effecting polymerization at from 20 to 100° C. and from1000 to 10,000 kPa have proven to be a suitable polymerization process.Under the polymerization conditions described, spiroketal formation wasnot observed.

The novel carbon monoxide copolymers can be processed by means ofinjection molding, blow molding, spinning, rotation molding, extrusionor spin coating. It is also possible to coat metallic, ceramic and othersurfaces, for example those of plastics materials.

Novel carbon monoxide copolymers which are suitable for the productionof fibers, films, moldings and coatings are in particular those whichare intended to be tough. Furthermore, they can be used as mixingcomponents in plastics, in particular in those which are intended to betough. In particular, the carbon monoxide/propylene terpolymersdescribed also provide an economical route to molding materials having athermoplastic elastomeric property profile.

EXAMPLES

General Polymerization Conditions

I. Binary Carbon Monoxide Copolymers

100 ml of dichloromethane and 35 mg (0.045 mmol) of the palladiumcompound [Pd(dppp)(NCCH₃)₂](BF₄)₂, and 0.25 ml (6.2 mmol) of methanolwere initially taken at a 0.3 l steel autoclave. A mixture of olefin (20g) and carbon monoxide (82,0×10⁵ Pa) was then polymerized at 25° C. for72 hours.

The temperature and the partial pressures of the monomers were keptconstant during the entire duration of the reaction. The polymerizationwas stopped by reducing the pressure to ambient pressure, methanol wasadded to the reaction mixture, the mixture was filtered, the solvent wasremoved from the filtrate and the polymer was isolated. For furtherpurification, the product was dissolved in dichloromethane (100 ml) andfiltered over a short silica gel column. The experimental parameters andthe polymer properties are as shown in Table 1.

Carbon monoxide/hept-1-ene Copolymer (Hp-CO) (Example 1)

¹H-NMR (CDCl₃): δ=0.85 (t, —CH₃, 3H); 1.10-1.70 (broad, —(CH₂)₄, OH),2.30-2.65 (broad, —CH, 1H); 2.70-3.20 (broad, —CH₂, 2H).

¹³C-NMR: δ=13.8; 22.2-23.4; 26.1-26.5; 28.7-31.7; 43.0-44.5; 45.0-46.0;207-209; 211-213; 214-215.

(C₈H₁₄O)_(n) (126.19)_(n): Calc. C, 76.14; H, 11.2. Found. C, 76.93; H,11.65.

Carbon monoxide/oct-1-ene Copolymer (Oc-CO) (Example 2)

¹H-NMR (CDCl₃): δ=0.85 (t, —CH₃, 3H), 1.17-1.70 (broad, —(CH₂)₅, 10H),2.39-2.60 (broad, —CH, 1H), 2.80-3.10 (broad, —CH₂, 2H).

¹³C-NMR: δ=13.9, 22.4, 26.9, 29.2, 30.0-3.15, 42.0-43.6, 44.2-45.5,207.1-208.4, 211.6-212.9, 213.5-214.8. (C₉H₁₆O)_(n) (140.22)_(n): Calc.C, 77.09; H, 11.50. Found. C, 77.40; H, 11.68.

Carbon monoxide/dodec-1-ene Copolymer (Dd-CO) (Example 3)

¹H-NMR (CDCl₃): δ=0.80 (t, —CH₃, 3H), 1.20-2.00 (broad, —(CH₂)₁₀, 10H),2.20-2.60 (broad, —CH, 1H), 2.80-3.10 (broad, —CH₂, 2H).

¹³C-NMR: δ=14.0, 22.6, 26.3-27.9, 28.3-29.5, 31.8, 42.0-43.5, 44.0-45.5,207.0-209.0, 211.5-212.5. 213-215.

(C₁₃H₂₄O)_(n) (196.33)_(n): Calc. C, 79.53; H, 12.32. Found. C, 78.62;H, 12.60.

Carbon monoxide/hexadec-1-ene Copolymer (Hd-CO) (Example 4)

¹H-NMR (CDCl₃): δ=0.90 (broad, —CH₃, 3H), 1.10-2.00 (broad, —(CH₂)₁₃,26H), 2.15-2.60 (broad, —CH, 1H), 2.81-3.22 (broad, —CH₂, 2H). ¹³C-NMR:δ=12.0, 20.0, 22.7, 27.1-31.4, 42.0-44.0, 45.0-46.0, 207.0 (broad),212.0 (broad), 215.8 (broad) (C₁₇ ^(H) ₃₂O)_(n) (252,44)_(n): Cal. C,80.89; H, 12.78. Found. C, 81.23; H, 13.39.

Carbon monoxide/octadec-1-ene Copolymer (Od-CO) (Example 5)

¹H-NMR (CDCl₃): δ=0.85 (t, 3H, —CH₃), 1.22-1.80 (broad, (CH₂)₁₅, 30H),2.20-2.60 (broad, —CH, 1H), 2.80-3.20 (broad, —CH₂, 2H).

¹³C-NMR: δ=14.1, 22.7, 27.1, 28.9-31.4, 31.9, 33.8, 41.2-42.5,43.5-44.6, 207.0 (broad), 212.0 (broad), 214.8 (broad).

(C₁₉H₃₆O)_(n) (280.49)_(n): Calc. C, 81.36; H, 12.94. Found. C, 81.75;H, 12.92.

Carbon monoxide/eicos-1-ene Copolymer (Ei-CO) (Example 6)

¹H-NMR (CDCl₃): δ=0.85 (t, 3H, —CH₃), 1.22-1.80 (broad, (CH₂)₁₅, 30H),2.20-2.60 (broad, —CH, 1H), 2.80-3.20 (broad, —CH₂, 2H).

¹³C-NMR: δ=14.1, 22.7, 27.1 28.9-31.4, 31.9, 33.8, 42.0-43.6, 44.2-45.6,207.5-208.5, 211.4, 213.0, 214.0-215.2. (C₂₁H₄₀O)_(n) (308.55)_(n):Calc. C, 81.22; H, 13.63. Found. C, 82.15; H, 13.65.

Copolymerization of ¹³CO with eicos-1-ene

Prepared by the same process as described above, with constant¹³CO-partial pressure and a reaction time of 24 h. ¹³C-NMR (CDCl₃):carbonyl-range δ=209.0-210.9, 211.7-212.6, 213.8-215.2 ppm.M_(w)=6.9×10³ g/mol, M_(w)/M_(N)=1.44.

II. Ternary Carbon Monoxide Copolymers

100 ml of dichloromethane, 0.25 ml of methanol and 35 mg (0.045 mmol)[Pd(dppp)(NCCH₃)₂] (BF₄)₂ and 10 g of 1-octadecene or 1-eicosene wereinitially taken as 0.3 l steel autoclave. 40 g of propylene or ethylene(10.5×10⁵ Pa) and carbon monoxide (82.0×10⁵ Pa) were fed in andpolymerized with mechanical stirring for 48 h at 25° C. The temperatureand the partial pressures of the monomers were kept constant during theentire duration of the reaction. The polymerization was stopped byreducing the pressure to ambient pressure and by adding an excess ofmethanol. The reaction mixture was filtered, the solvent was removedfrom the filtrate and the polymer was isolated, washed with methanol(200 ml), filtered, and dried under reduced pressure. The furtherexperimental parameters and the polymer properties are as shown in Table2.

Carbon monoxide/propylene/octadec-1-ene-terpolymer 1 (ODPCO 1) (Example7)

¹H-NMR (CDCl₃): δ=0.80 (t, —CH₃ (Od-CO)), 1.00 (broad, —CH₃, (P—CO)),1.12-1.99 (broad), 2.29-2.50 (broad), 2.89-3.15 (broad).

¹³C-NMR: δ=14.1, 16.9, 22.4, 22.7, 28.9-29.9, 31.7, 33.7, 40.1 (broad),44.5 (broad), 207.0 (broad), 211.8 (broad), 214.8 (broad).

Carbon monoxide/propylene/octadec-1-ene-terpolymer 2 (ODPCO 2) (Example8)

¹H-NMR (CDCl₃): δ=0.77 (t, —CH₃ (Od-CO)), 1.00 (broad, —CH₃ (P—CO)),1.10-2.0 (broad), 2.30-2.40 (broad), 2.80-3.15 (broad).

¹³C-NMR: δ=13.9, 16.3, 22.4, 22.7, 28.9-29.9, 31.8, 33.7, 41.2 (broad),44.6 (broad), 207.4 (broad), 211.9 (broad), 215.4 (broad).

Carbon monoxide/propylene/eicos-1-ene-terpolymer (EiPCO) (Examples 9 and10)

¹H-NMR (CDCl₃): δ=0.77 (—CH₃), PCO), 1.00 (broad, 3H, Od-CO—H₃),1.12-1.99 (broad), 2.29-2.50 (broad), 2.89-3.15 (broad).

The molecular weights M_(w) and the molecular weight distributionsM_(w)/M_(n) were determined by gel permeation chromatography (GPC),based on a polystyrene standard.

¹H-NMR and ¹³C-NMR-measurements were carried out using the Bruker AMX500 or AC 200 spectrometer.

IR-measurements were carried out on the Bruker IFS66V spectrometer.

The DSC data were determined using the Perkin-Elmer DSC-7 apparatus at aheating rate of 10° C./min.

The melting points were likewise determined with the aid of apolarization microscope. The heating rate was set at 10° C./min.

The contact angle measurements on water drops (bidistilled, γN=72 mN/m)applied to films of copolymer material were carried out by the sessiledrop technique using a G 40 goniometer from Krüss, Hamburg, which wasequipped with a video system, an image processor (G 1041) and the PDA 10software.

The copolymer films were produced from solution (1.0% w/w-, CH₂Cl₂) byevaporating the solvent on a rotating glass sheet (spin-casting) at 15to 25° C. (for carbon monoxide/ethylene copolymers, a 0.5% w/w solutionin 1,1,1,3,3,3-hexafluoro-2-propanol was used). The solvent residueswere removed by evacuation for one hour. For the contact anglemeasurement, the tangent method at 20° C. was used (cf. R. J. Good andR. R. Shomberg, “Surface and Colloid Science”, Vol. 11, ExperimentalMethods, Plenum Press, New York, 1979). The contact angle was determinedon a drop with a measured frequency of 1 Hz over 5 seconds. The valuesdescribed are mean values of 15 individual measurements on three dropsaltogether. The accuracy of measurement was in the range of ±2.0°.

TABLE 1 Copolymerization of carbon monoxide with 1-alkenes^(a)) Exam-M_(w) ^(b)) vC═O T_(g) ^(d)) Yield ple Copolymer 1-Alkene (g/mol)M_(w)/M_(n) ^(b)) (cm⁻¹) (° C.) T_(m)° C., (ΔH_(f)J/g)]^(d)) (g) 1 Hp-CO1-Heptene 2.8 × 10⁴ 1.69 1705 −24.0 −7.0 (broad)^(f)) 2.6 2 Oc-CO1-Octene 2.9 × 10⁴ 1.76 1705 −33.0 —^(e)) 2.5 3 Dd-CO 1-Dodecene 1.9 ×10⁴ 1.78 1711 −59.8 —^(e)) 1.6 4 Hd-CO 1-Hexadecene 2.3 × 10⁴ 1.68 1712—^(e)) 13.0^(f)) 1.3 5 Od-CO 1-Octadecene 2.6 × 10^(4c)) 1.53^(c)) 1709—^(e)) 19.3, 32.3 (103) 8.5 6 Ei-CO 1-Eicosene 2.1 × 10^(4c)) 1.67^(c))1707 —^(e)) 28.9 (51.0), 41.2 (65.8) 8.0 ^(a))Polymerization conditions:solvent: dichloromethane (100 ml); activator (methanol)/Pd-molar ratio:140/1; polymerization temperature: 25° C.; carbon monoxide partialpressure: 82.0 × 10⁵ Pa; 1-alkene: 20 g; reaction time: 72 h.^(b))Determined by means of GPC (with polystyrene as referencestandard). ^(c))Confirmed by further analysis systems (differentialrefractometer, Water Model 510; differential viscometer, Viscothek ModelH 502, GPL Win-Software): Od-CO: M_(w) (M_(w)/M_(n)) = 6.9 × 10⁴ (1.88);Ei-CO: M_(w) (M_(w)/M_(n)) = 5.7 × 10⁴ (1.97). ^(d))Glass transitiontemperature (T_(g)], melting point [T_(m)] enthalpy of fusion (ΔH_(f))(determined from the second run with the aid of the tangent method.^(e))Not determined. ^(f))Determined by polarization microscopy (Example1: heating rate 30° C./min).

TABLE 2 Terpolymerization examples^(a)) Amount of C₁₈-/C₂₀- 1-alkeneProportion of starting C₁₈-/C₂₀- material M_(w) ^(b)) vC═O T_(g)1-alkene Yield Ex. Terpolymer (g) (g/mol) M_(w)/M_(n) ^(b)) (cm⁻¹) (°C.)^(d)) [T_(m) ° C., (ΔH_(f)J/g)]^(d)) (mol-%) (g)  7 OdPCO 1  5.0 1.63× 10⁵ 1.84 1714 19.3 81.0 (20.7) 13.0  8.0  8 OdPCO 2 14.0 6.83 × 10⁴1.43 1708 −15.4 12.9 (66.0) 30.0 10.0  9 EiPCO 10.9 5.66 × 10⁴ 1.90 1705—^(c)) 9.12 (16.5); 33.0 (118.0) 21.0  2.0 10 OdECO 10.0 —^(c)) —^(c))1691 —^(c)) 84.52 (24.9), 185 (20.8) —^(c))  5.5 ^(a))Polymerizationconditions: solvent: dichloromethane (100 ml); activator(methanol)/Pd-molar ratio: 140/1; polymerization temperature: 25° C.;carbon monoxide partial pressure: 82.0 × 10⁵ Pa; 1-alkene: 40 g;ethylene partial pressure 10.5 × 10⁵ Pa; reaction time: 48 h.^(b))Determined by means of GPC (with polystyrene as referencestandard). ^(c))The polymer is insoluble. ^(d))Glass transitiontemperature (T_(g)), melting point (T_(m)), enthalpy of fusion (ΔH_(f))(determined from the second run with the aid of the tangent method).^(e))Not determined. ^(f))Calculated on the basis of the ¹H-NMR spectra.

We claim:
 1. A linear, thermoplastic, elastomeric copolymer of carbonmonoxide, at least one olefinic C₂- to C₄-monomer and at least oneolefinic C₆- to C₂₀-monomer, which has an average molecular weight M_(w)greater than 163,000 g/mol and a T_(g) value of less than 20° C.
 2. Alinear, thermoplastic, elastomeric copolymer as claimed in claim 1,wherein the olefinic C₂- to C₄-monomer used is propylene.
 3. A processfor the preparation of a linear, thermoplastic, elastomeric copolymer ofcarbon monoxide and at least one olefinic C₇- to C₂₀-monomer having anaverage molecular weight M_(w) greater than 15,000 g/mol and a Tg valueof less than −20° C., wherein the copolymerization of carbon monoxidewith olefinic monomers is carried out in a virtually alcohol-free oranhydrous polymerization medium in the presence of a catalyst whoseactive material is formed from A) a metal complex of the formula (I)

 where: M is palladium E¹ and E² are each phosphorus Z is methylene,1,2-ethylene, 1,3-propylene, 1,4-butylene, 1,3-disilapropylene,ethylidene, 2-propylidene, diphenylmethylene or ortho-phenylene, R¹ toR⁴ are substituents selected from the group consisting of C₁- toC₂₀-organocarbon radicals and C₃- to C₃₀-organosilicon radicals, itbeing possible for the radicals to contain an element or a plurality ofelements of group IVA, VA, VIA and VIIA of the Periodic Table ofElements, L¹ and L² are formally uncharged Lewis base ligand X isperchlorate, sulfate, phosphate, nitrate, carboxylate, conjugated anionsof organosulfonic acid, tetrafluoroborate, tetraphenylborate,tetrakis(pentafluorophenyi)borate, hexafluorophosphate,hexafluoroarsenate or hexafluoroantimonate, m and n are each 1 or 2 andm×n=2 and B) an activator component which contains a hydroxyl group inthe molecule and which is used in an amount of from 0 to 500 moleequivalents, based on M in (I) wherein the individual catalystcomponents are brought into contact to generate the catalyst before thecatalyst is brought into contact with the monomers.
 4. A process for thepreparation of a linear, thermoplastic, elastomeric copolymer of carbonmonoxide, at least one olefinic C₂- to C₄-monomer and at least oneolefinic C₆- to C₂₀-monomer, wherein the copolymerization of carbonmonoxide with olefinic monomers is carried out in a virtuallyalcohol-free or anhydrous polymerization medium in the presence of acatalyst whose active material is formed from A) a metal complex of theformula (I)

 where: M is palladium E¹ and E² are each phosphorus Z is methylene,1,2-ethylene, 1,3-propylene, 1,4-butylene, 1,3-disilapropylene,ethylidene, 2-propylidene, diphenylmethylene or ortho-phenylene, R¹ toR⁴ are substituents selected from the group consisting of C₁- toC₂₀-organocarbon radicals and C₃- to C₃₀-organosilicon radicals, itbeing possible for the radicals to contain an element or a plurality ofelements of group IVA, VA, VIA and VIIA of the Periodic Table ofElements, L¹ and L² are formally uncharged Lewis base ligands X isperchlorate, sulfate, phosphate, nitrate, carboxylate, conjugated anionsof organosulfonic acid, tetrafluoroborate, tetraphenylborate,tetrakis(pentafluorophenyl)borate, hexafluorophosphate,hexafluoroarsenate or hexafluoroantimonate, m and n are each 1 or 2 andm×n=2 and B) an activator component which contains a hydroxyl group inthe molecule and which is used in an amount of from 0 to 500 moleequivalents, based on M in (I).
 5. A process as claimed in claim 4,wherein the carbon monoxide copolymer has an average molecular weightM_(w) greater than 68,000 g/mol.
 6. A fiber, film, molding or coatingproduced from a carbon monoxide copolymer obtained by the process asclaimed in claim
 3. 7. A fiber, film, molding or coating produced from acarbon monoxide copolymer as claimed in claim
 1. 8. A copolymer asclaimed in claim 1, which is a terpolymer, and wherein the content ofC₂- to C₄-monomer is from 10 to 50 mol % based on the copolymer.